Method of treating crude oil or petroleum



Dec. 15,1925. 1,566,008

C. G. HINRICHS METHOD OF TREATING CRUDE OIL OR PETROLEUM Filed Nov. 23,1918 T. ill

CARL Gr. HINRICHS, OF ST. LOUIS, MISSOURI.

METHOD OF TREATING CRUDE OIL 0R PETROLEUM.

Application filed November 23, 1918. Serial No. 263,896.

To (ZZZ whom it may concern:

Be it known that I, CARL G. HINRICHS, a citizen of the United States,residing at St. Louis, Missouri, have invented a certain new and usefulMethod of Treating Crude Oil or Petroleum, of which the following is afull, clear, and exact description, such as will enable others skilledin the art to which it appertains to make and use the same, referencebeing had to the accompanying drawings, forming part of thisspecification.

My invention relates to a new and useful method or process of treatingcertain crude oils which, when drawn from the earth, contain a certainpercent or content of waste substance or matter foreign to marketablepetroleum, the principal object of my invention being to provide apracticable and inexpensive method or process for separating fromso-called roily oils or natural petroleum, practically all the oilsuitable for commercial uses.

In certain localities or oil fields, the crude oil taken from the groundcontains brine and other foreign matter, the volume of which veryfrequently exceeds the limit or commercial allowance established foracceptance by pipeline operators or refiners. In certain fields, thisvolume of foreign matter runs as high as fifty percent and pipe linesrefuse to accept crude oil containing over three percent of foreignmatter. Where the crude oil is acceptable it is very fre--- quentlystored for a considerable eriod of time in tanks where a portion 0 theforeign matter separates from the merchant- -able oil by gravitating tothe bottom of the tank and where such action takes place, the

accumulation of foreign substance is in the form of a relatively thick,brown-colored, salve-like mass, and is generally known as bottomsettlings. This mass contains a high percent of petroleum, in additionto brine, organic matter, and very frequently silt, and obviously onlarge tank farms, the mass accumulates in large quantities and muchtime, labor and consequently expense is involved in getting rid of it.

Wells in certain fields produce what is known as roily oil, that is, oilwhich contains a sufiicient percentage of foreign substance to give it aroily appearance. This oil mayby the ordinary settling process result ina considerable portion of good merl chantable petroleum, or by simplyheating the oil an increased amount of marketable product may beproduced, but these methods have not in practice proven satisfactoryandthe storage of large quantities of oil involves the investment ofconsiderable capital in storage tanks and oil handling equipment.

Under the microscope, the so-called bottom settlings appear as anemulsion. The water or brine mixed with the emulsion appears to greatlyinfluence the stability of the latter. Some brines I have found areslightly alkaline in their nature due to loss of carbonic acid from thebicarbonates of the brine and presence of phosphates and silicates ofthe alkalies contained therein. By the treatment of bottom settlingswith a salt having a slight acid reaction, as, for instance, theso-called bi-salts or mono sodium phosphate, a separation of the oilfrom the foreign substances is possible. In practice I have separatedoil in the manner just described and upon alkalinizing the mass, thesame has again become roily. This indicates that the permanence of suchemulsions depend greatly on the slight alkalinity or, acidity of thebrines, which latter conditions may be due to bicarbonates or to theacids occurring in some petroleums having a composition similar to oleicacid. Thus it is evident that the alkalinity of the emulsion may beoverdone and the object of separation defeated.

Some oils may be treated by nitrates, for instance, aluminum nitrates,and a separation effected by warming the mass to reduce its viscosity ora sufiicient amount of alkali may be added to form the aluminate of thealkali metal and its nitrate, and separation thus effected.

In experiments I have used ethyl sulphates, salts of amyl sulphuricacid, sodium potassium or ammonium cyanides, fluosilicates, phosphates,fiuoborates, and borates in treating the bottom settlings either inslightly acid or alkaline conditions of the mass in effecting thedesired separation; To be more specific, I have used the sodium calciumsalts of ethyl sulphuric acid, formerly known as sulphovinic acid, whichacid, SO, (G H H results from the action of sulphuric acid on alcohol.This acid neutralized with sodium carbonate gives sodium ethyl sulphateNA(C H )SO and when neutralized with ime gives calcium ethyl sulphateGa- [(C H )SO,] I have also used the calcium and sodium salts of amylsulphuric acid SO (C H ,)H, the calcium salt having the formula Ca[SO (CI-I and the sodium salt having the formula NaSO; 5, 11)- I have alsoused ethyl sulphuric acid to form a potassium salt having the formula.K(C H )SO which is effective upon certain roily oils.

I have also found that acid sodium phos phate (NaH PO and acid calciumphosphate (CaH (PO each neutralizes the sodium carbonate of the brinedissolving; the brine acids which hold the emulsion together.

I have also used sulphocyanides produced by potassium and lime salts,KCNS and Ca(CNS) respectively. Since the emulsion often results from thepresence of mineral iron salts, usually basic, when such emulsions aretreated with sulphocyanides either of lime or the alkalis, sulphocyanideofiron is formed which is soluble not only in the brine but also in theoil. This partial solubility of the iron in both liquids gives a clearclean separation of the brine from the oil without any deposit of ironsalts between the two. The salts of amyl sulphuric or ethyl sulphuricacids act similarly to form corresponding soluble iron salts.

All of the above mentioned salts may be applied to the oil either aspowder or in solution.

I have also found that halogen addition products of such liquid fattyacids as ricinoleic acid or oleic acid have the same properties and thatin some cases the acid as such may be employed and in other cases theacids may be brominated or chlorinated to produce salts, which actionsincrease the value of the compounds for reducing the viscosity of themedium and effecting a sepa ration of the oil. The formation of thechlorine addition product of oleic acid may be expressed by the formula(1 11 0131 and this plus sodium (NaOH) will give the salt of chlorineaddition product Nafi I-I Ofil H-I O). Likewise I have Used halogensubstitute products of rosin. Unsaturated fatty acids of relatively highmolecular weight have a reducing effect on the surface tension existingbetween the minute globules and the brine medium, and by forming thesubstitution products of unsaturated fatty acids this reduction of thesurface tension can be increased. This method is very economical byvirtue of the fact that chlorine costs less to produce than oleic orother fatty non-saturated acid and the consumption of alkali is reducedper unit of salt produced.

In practicing my invention, I dissolve in water, preferably hot, theagent determined upon as cheapest and best suited. for the particularoil,- then warm the oil to approximately the desired temperature, whichlatter is developed by experiment, then inject the hot solution in theamount of about two or three percent and agitate the mass with air,steam, natural gas, mechanically or by pumping the oil'from the top ofthe tank or container and injecting it into the top or vice versa.

In some instances, the agent can be dissolved in carbon tetrachloride,in which instance, it may be found desirable to incorporate therewithoils, waxes, higher alcohols such as are obtained from waxes, fusel oil,oils obtained in distillation of coal or in the production of oil gas,and where such practice occurs the viscosity of the petroleum is greatlyinfluenced due to the reducing of the melting point of some of thehigher boiling fractions contained in said petroleum. In such instances,I find it desirable to place the solution on the surface of the oil tobe treated, and under such conditions I have noted that the oil in manyin: stances, breaks gradually Without warming.

In the drawings, I have shown a diagrammatic view partly in section ofan apparatus designed for carrying out my improved method, and referringby numerals to said drawings, 10 designates a tank or container for theoil, and.11 the tank or container for the composition to be utilized intreating the oil. Leading from the tank 11 into the oil tank 10 is apipe 12, the

length of which within the oil tank is perforated in order that thecomposition from said tank 11 will be discharged into the oil tank injet form.

Located in pipe 12 is an injector 13 to which leads a pipe 14 from asuitable source of steam supply, Leading from a source of steam supplydownwardly into oil tank 10 is a pipe 15 and said pipe leads to a steaminjector 16 which is located in the bottom of said tank 10. Leading fromsaid injector 16 upwardly within tank 10 is a pipe 17, the sameterminating in the upper portion of said oil tank.

Mounted for rotation on the end of this pipe 17 is a spray device 18,preferably of that type which is propelled or rotated by the force ofthe jets issuing therefrom.

' When this form of apparatus is utilized, steam is admitted to pipe 14connected to the injector 13 and the action of the latter draws thetreating agent from tank 11 and forces the same through pipe 12, saidagent being discharged from the apparatus in the leg of said pipe in oiltank 10. Thus the treating agent is heated and introduced into the bodyof oil contained in tank 10 and when steam is turned on through pipe 15,it will discharge intothe injector 16, thereby drawing the oil and thetreating agent into said injector and the steam heated mixture will nowpass through pipe 17 and be dis-- charged from the jet openings in thearms 7 stance from the commercially pure oil. The

steam is now out off from pipes Hand 15 and the oil in tank 10 ispermitted to stand for a certain length of time, whereupon thecommercially pure oil will rise to the top while the silt, brine, andother foreign matter will settle to the bottom. Between the body of oiland silt and brine will accumulate a relatively thin stratum of organicmatter. The relatively pure oil can now be drawn from tank 10 leaving inthe bottom thereof the organic matter and silt and,

brine from which practically all of the oil has been extracted.

I do not wish to be understood as limiting myself to the exact form ofapparatus, herein shown and described, for practicing my improvedmethod, for obviously the method may be carried out with various otherforms of apparatus, the only essential feature being a thoroughcommingling of the treating agent with the oil or material to be treatedand permitting the latter to stand until separation has taken place.

Having thus described my invention, what I claim is:

1. The hereindescribed method of treating bottom settlings to separatethe oil.

2. The hereindescribed method of treating bottom settlings to separatethe oil therefrom consisting in 'mixing with said bottom settlings asolution of a halogen addition product of a liquid fatty acid in carbontetrachloride, and then permitting the mass to stand until the oilseparates. and rises to the. to

3. The herelndescribed process of treating natural petroleum emulsionswhich con sists in thoroughly mixing therewith a chlorine additionproduct of a liquid fatty acid in suflicient quantity to effect aseparation of the oil from the brine and foreign matter of. theemulsion.

4. The hereindescribed process of treating natural petroleum emulsionswhich consists in thoroughly mixing therewith a salt of a chlorineaddition product of a liquid fatty acid in sufiicient quantity to effecta separation of the oil from the brine and foreign matter of theemulsion.

5. The hereindescribed method of treating petroleum emulsions whichconsists in thoroughly mixing therewith a chlorine addition product of aricinoleic' acid in sufficient quantity to effect a separation of theoilfrom the brine and foreign matter of the emulsion.

- 6. The method of treating petroleum emulsions which consists in mixingtherewith a halogen addition product of ricinoleic acid in sufficientquantity to effect a separation of the oil from the brine andforeign'matter of the emulsion.-

In testimony whereof I hereunto aflix my signature this 20th day ofNovember, 1918.

CARL G. HINRICHS.

